CN106748619A - A kind of technique that propane is refined from the feed stream comprising propane and dimethyl ether - Google Patents
A kind of technique that propane is refined from the feed stream comprising propane and dimethyl ether Download PDFInfo
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- CN106748619A CN106748619A CN201611161372.8A CN201611161372A CN106748619A CN 106748619 A CN106748619 A CN 106748619A CN 201611161372 A CN201611161372 A CN 201611161372A CN 106748619 A CN106748619 A CN 106748619A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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Abstract
The present invention relates to a kind of technique that propane is refined from the feed stream comprising propane and dimethyl ether, the feed stream comprising propane and dimethyl ether is carried out into dimethyl ether removing treatment successively, washing process and dewater treatment, extracting rectifying is carried out to the raw material comprising propane and dimethyl ether as extraction distillation solvent using organic oxygen-containing compound or its aqueous solution in dimethyl ether removing section, the primary purification propylene oxide stream obtained through extracting rectifying is washed into subsequent washing section, wash away the organic oxygen-containing compound that wherein azeotropic is formed and the micro dimethyl ether for remaining, it is last to obtain the logistics comprising dimethyl ether and organic oxygen-containing compound and obtain gas phase at the top of washing section in dimethyl ether removing section bottom to refine propylene oxide stream, refined bromopropane product is obtained after its condensed and dehydration.Compared with prior art, the refined bromopropane product that the present invention is obtained can be used as the raw material of dehydrogenating propane or light hydrocarbon cracking, it is also possible to make liquefied petroleum gas, the value of the raw material is thus greatly improved.
Description
Technical field
The present invention relates to propane purifying technique, and in particular to a kind of to be refined from the feed stream comprising propane and dimethyl ether
The technique of propane.
Background technology
Such as oxygenatedchemicals alkene (OTO), methanol-to-olefins (MTO) and oxygenatedchemicals are converted in oxygenatedchemicals
In various industrial process such as gasoline processed, propane and dimethyl ether would generally be included in produced reaction effluent, and due to diformazan
The boiling point (being -24.8 DEG C under normal pressure) of ether is more or less the same with the boiling point (being -42.0 DEG C under normal pressure) of propane, in these reaction outflows
During, the two is generally present in same logistics the subsequent fine cut of thing, i.e., be difficult two by common distillation process
Person separates.Accordingly, it would be desirable to further treatment includes the logistics of propane and dimethyl ether therefrom to refine propane.
Typically, during oxygenatedchemicals alkene, due to as feedstock and/or as intermediate product
The dimethyl ether of formation is not fully converted to target product, and due to oxygen-containing in lighter hydrocarbons logistics in actual subsequent separation process
The removal effect of compound is not ideal enough, to cause and generally comprise dimethyl ether in the lighter hydrocarbons logistics comprising propane.
For both propane and dimethyl ether, dimethyl ether can serve as the reaction raw materials of oxygenatedchemicals alkene, third
Alkane then can serve as the raw material of dehydrogenating propane or light hydrocarbon cracking device, it is also possible to make liquefied petroleum gas, and they are all have height attached
Value added product.But dehydrogenating propane or light hydrocarbon cracking device have strict limitation to the diformazan ether content in raw material propane, such as require
Total oxide (including dimethyl ether, methyl alcohol and acetone etc.) content≤100mg/kg in raw material propane, and require that wherein methyl alcohol contains
Amount≤30mg/kg, and State Administration for Quality Supervision and Inspection and Quarantine then prohibites and dimethyl ether is blended in civil LPG
(quality inspection is write (2008) No. 17《Notice on cylinder filling relevant issues》), thus in oxygenatedchemicals olefin hydrocarbon
The logistics comprising propane and dimethyl ether of by-product can not be directly used as the raw material of dehydrogenating propane or light hydrocarbon cracking device, can not
It is directly used as liquefied petroleum gas.
In order to improve oxygenatedchemicals conversion as in oxygenatedchemicals olefin hydrocarbon by-product comprising propane and dimethyl ether
Logistics value, be such as allowed to can be used as the raw material of dehydrogenating propane or light hydrocarbon cracking device and/or as liquefied petroleum gas,
Be necessary that therefrom removing dimethyl ether obtains the refined logistics comprising propane, at the same can also reclaim dimethyl ether be re-used as it is oxygen-containing
The reaction raw materials of compound conversion process.
WO 03/020678A2 are related to a kind of method that dimethyl ether is removed from olefin stream, wherein the olefin stream is obtained
From oxygenatedchemicals olefin hydrocarbon, the olefin stream obtains the logistics comprising propane and dimethyl ether, the logistics by rectifying
In containing the C4+ and the hydrocarbon of higher boiling point no more than 5wt%, the then logistics further removes diformazan in extractive distillation column
Ether, wherein extraction distillation solvent are polar solvent of the atmospheric boiling point higher than 38 DEG C, and the extractive distillation column contains rectifying section and carries
Evaporate section.
CN101076507B discloses a kind of side that oxygen-containing organic compound is removed from the mixture of various hydrocarbon compounds
Method, lighter hydrocarbons and the gaseous mixture being made up of hydrocarbon and oxygen-containing organic compound enter in extraction distillation column, and extractive distillation solvent is adopted
With monohydric alcohol or the aqueous solution of dihydroxylic alcohols or 1-METHYLPYRROLIDONE or 1-METHYLPYRROLIDONE, with it, being steamed from extraction
Evaporate in the hydrocarbon products that top of tower leaves without oxygen-containing organic compound, tower reactor discharge oxygen-containing organic compound, extractive distillation solvent
With the mixture of residual hydrocarbon, wherein extractive distillation solvent can partially or completely be regenerated, and be recycled back into extraction distillation column.
But, there is azeotropism (such as first between propane and the organic oxygen-containing compound for being typically used as extractive distillation solvent
Alcohol there is azeotropic with propane, and in 1750KPa absolute pressures, 50.5 DEG C of azeotropic temperature contains methyl alcohol 0.77wt% in azeotropic mixture), because
This applies above two method, although can remove the dimethyl ether in the logistics comprising propane and dimethyl ether, but in extracting rectifying
In the bromopropane product that column overhead is obtained, still containing the larger amount of organic oxygen-containing compound as extraction distillation solvent, propane is produced
Product can not still be directly used as the raw material of dehydrogenating propane or light hydrocarbon cracking device, can not be directly used as liquefied petroleum gas.
The content of the invention
The purpose of the present invention is exactly to provide total in a kind of propane product for the defect for overcoming above-mentioned prior art to exist
The low technique that propane is refined from the feed stream comprising propane and dimethyl ether of oxide content.
The purpose of the present invention can be achieved through the following technical solutions：It is a kind of from the raw material thing comprising propane and dimethyl ether
The technique that propane is refined in stream, the technique includes dimethyl ether removing treatment, washing process, the part of dewater treatment three successively；
The dimethyl ether removing treatment is completed in dimethyl ether removing section, and dimethyl ether removing section is divided into part, middle part
With lower part, comprise the following steps：Feed stream comprising propane and dimethyl ether is from its top feed of lower part, and extracting rectifying is molten
Its top feed of agent logistics therefrom part, refined its top feed of the propylene oxide stream from upper part of backflow, through extracting rectifying on top
The top divided obtains primary purification propylene oxide stream, and lower section bottom obtains the logistics comprising dimethyl ether and extraction distillation solvent, should
A logistics part is circulated through tower reactor reboiler, and remainder delivers to next workshop section, that is, send into oxygenatedchemicals alkene dress
Put, the raw material as course of reaction；
The washing process is completed in washing section, is comprised the following steps：Primary purification propylene oxide stream is from washing section bottom
Charging, current obtain the refined propylene oxide stream of gas phase, water through continuous flow upstream washing from washing section its top feed at the top of washing section
A section bottom is washed to obtain washing water logistics；
The dewater treatment is completed in point water return tank, is comprised the following steps：The refined propylene oxide stream of gas phase is passed sequentially through
Overhead condenser and point water return tank, obtain being dehydrated refined propylene oxide stream after dehydration, and it passes through the propane booster pump supercharging that flows back
Afterwards, the top of part in dimethyl ether removing section is partly refluxed to, remaining is produced as refined bromopropane product logistics, point water return tank
The current of bottom discharge removing.
According to the present invention, wherein at least is combined with dimethyl ether removing section and washing section, according to the operator scheme：In dimethyl ether
Removing section is acted on by the extracting rectifying of oxygen-containing organic compound or its aqueous solution, raw material thing of the removing comprising propane and dimethyl ether
Dimethyl ether in stream, thus obtains the logistics comprising dimethyl ether and organic oxygen-containing compound in dimethyl ether removing section bottom；In water
The organic oxygen-containing compound that section is washed by continuous flow upstream washing removing azeotropic from the propylene oxide stream of primary purification is micro- with residual
Amount dimethyl ether, with the dimethyl ether in more thoroughly removing feed stream and the preferably refined feed stream, thus in washing
Phase propane logistics after being refined at the top of section, and produce one washing water logistics in washing section bottom.It is preliminary in order to prevent
Refined propylene oxide stream condense in washing section, and for the temperature of current of washing, preferably less than primary purification propylene oxide stream does not enter water
Wash the temperature of section.
According to the present invention, in leaving the phase propane logistics at the top of washing section, containing with aqueous water into balance water vapour,
After being condensed through overhead condenser, there will be free water to separate out, the method that the part moisture is removed in point water return tank can be used directly
Gravitational settling, or be dehydrated by coalescer.
In order to reduce the organic oxygen-containing compound content in primary purification propylene oxide stream as far as possible, so as to reduce for washing
The consumption of current, the feed entrance point of extraction distillation solvent is preferably located at the 3-5 block theoretical plates of dimethyl ether removing section.
According to the present invention, the technique can be operated using single column, and wherein washing section is located at the upper of dimethyl ether removing section
Side；
Described washing water logistics directly flow to the top of part in dimethyl ether removing section from washing section bottom；
Or hydrops groove and riser, the primary purification third are set between described dimethyl ether removing section and washing section
Alkane logistics enters washing section bottom by riser, and current and primary purification propylene oxide stream carry out continuous flow upstream water in washing section
Wash, the washing water logistics that washing section bottom obtains remove part in section by outer row after the collection of hydrops groove or part overflow to dimethyl ether
Top.
Because the separation mass-transfer efficiency of extracting rectifying is relatively low, and the separating effect for needed for reaching, the present invention needs certain
Number of theoretical plate, it means that knockout tower needs packed height higher or number of actual plates, in commercial Application for safety and
Equipment builds the convenience installed, it is necessary to reduce the height of knockout tower.Now, the present invention can be operated using double tower；
Wherein dimethyl ether removing section is arranged in the second tower, washing section is arranged in the first tower, and washing section bottom obtains
Washing water logistics outside arrange；
Or, the lower part and middle part of dimethyl ether removing section are arranged in the second tower, dimethyl ether removes the top of section
Divide and washing section is arranged in the first tower, washing section is located at the top of part in dimethyl ether removing section, and in washing section and diformazan
Ether removing section sets hydrops groove and riser between top point, wherein leaving the primary purification third of atop part in dimethyl ether removing section
Alkane logistics enters the bottom of washing section by riser, and washing section bottom is collected by collecting tank and arranged outside the washing water logistics for obtaining,
After the intersegmental liquid phase propylene oxide stream of the first tower tower reactor is pressurized with intersegmental liquid phase propane booster pump, the removing of the second tower dimethyl ether is added to
The top of part in section.
Described washing water logistics mix with the current of removing discharges as outer row washing water logistics.
Described outer row's washings stream portions or after all mixing with extraction distillation solvent logistics into dimethyl ether removing
The top of part in section, or described washings stream portions or after all mixing with extraction distillation solvent logistics into diformazan
The top of part in ether removing section；Or the current of removing partly or entirely mix with extraction distillation solvent logistics after into diformazan
The top of part in ether removing section.
Described extraction distillation solvent logistics is organic oxygen-containing compound logistics or its aqueous solution logistics, and extracting rectifying is molten
Organic oxygen-containing compound in agent logistics is selected from one or more mixture in methyl alcohol, ethanol, isopropanol, acetone, it is preferable that
The organic oxygen-containing compound is methyl alcohol and/or acetone.It is described water-soluble when with organic oxygen-containing compound aqueous solution form application
Mass content >=the 85wt% of the organic oxygen-containing compound of liquid；Preferably at least 93wt%；The organic oxygen-containing compound it is water-soluble
Liquid logistics can be mixed to get by organic oxygen-containing compound logistics with partly or entirely outer row's washing water logistics.
The described feed stream comprising propane and dimethyl ether, does not require, and wherein may be used substantially for propane content
With, the example very strong to the diformazan ether content adaptability of feed stream comprising relatively broad range of diformazan ether content, i.e. the inventive method
The mass fraction of the dimethyl ether in the feed stream comprising propane and dimethyl ether is 1~60wt% as described, preferably 2~
45%.
In principle, it is transformed that the feed stream comprising propane and dimethyl ether can come from any suitable oxygenatedchemicals
Journey, as long as can wherein be produced comprising propane and dimethyl ether such that it is able to pass through diformazan in reaction effluent segmentation subtractive process
The related logistics that ether removing is further processed.For example, the feed stream comprising propane and dimethyl ether can come from containing
Oxygen compound olefin hydrocarbon, in the case, in addition to propane and dimethyl ether, other is may also contain in the feed stream
Component, such as component of carbon two, propylene component and the component of carbon four.
According to the present invention, during whole operation, according to the determination of this area routine operation and each lever piece can be selected
Interior operating pressure, operation temperature and reflux ratio, usually, remove in section and washing section in the dimethyl ether, operate absolute pressure
Power can be 1.1~3.5MPa, preferably 1.3~3.0MPa；Operation temperature is 31~198 DEG C, preferably 38~165 DEG C, reflux ratio
It is 0.3~2.5, preferably 0.5~1.9.In preferred operating pressure and operating temperature range, overhead condenser can use cooling
, used as low-temperature receiver, tower reactor reboiler can be with low-pressure steam as thermal source, so as to make the public work grade of operating system optimal for water.
The theoretical cam curve of the dimethyl ether removing section is 10~26 pieces, preferably 12~20 blocks theoretical trays；The water
It is 2~6 pieces, preferably 3~4 blocks theoretical trays to wash the theoretical cam curve of section.
The quality stream of the organic oxygen-containing compound in the extractant stream and the feed stream comprising propane and dimethyl ether
Amount is than being 0.5~8, preferably 0.7~6；The current are with the mass flow ratio comprising propane and the feed stream of dimethyl ether
0.15~2, preferably 0.25~1.
Dimethyl ether in view of removing can continue on for conversion process of oxocompound, organic oxygen-containing compound or its is water-soluble
Liquid can be the raw material of conversion process of oxocompound, so that extraction distillation solvent is easier to obtain, and it is so resulting
The solution comprising dimethyl ether and organic oxygen-containing compound can directly return conversion process of oxocompound continue react so that
Running cost can significantly be saved and conversion process of oxocompound feed stock conversion higher can be realized.
Compared with prior art, beneficial effects of the present invention are embodied in following several respects：
(1) total oxide content in the refined propane of gained can be less than 100mg/kg, and wherein methanol content can be less than
30mg/kg, so that the product can be not only used for liquefied petroleum gas, it is also possible to make the raw material of dehydrogenating propane or light hydrocarbon cracking device, enter
And make the significantly upgrading of the logistics comprising propane and dimethyl ether of by-product in conversion process of oxocompound；
(2) due to can be by the use of the raw material of conversion process of oxocompound and/or product as extraction distillation solvent
Organic oxygen-containing compound, and the solution comprising dimethyl ether and organic oxygen-containing compound for being obtained can directly return it is oxygen-containing
Compound conversion process is further used as raw material, therefore, completely not due to increasing propane using different extraction distillation solvents
The cost of material of subtractive process, and even further increase raw material availability or the conversion of conversion process of oxocompound
Rate.
Brief description of the drawings
Fig. 1 is the first process schematic representation of the invention；
Fig. 2 is second process schematic representation of the invention；
Fig. 3 is the third process schematic representation of the invention；
Fig. 4 is the 4th kind of process schematic representation of the invention；
Fig. 5 is the 5th kind of process schematic representation of the invention.
In the drawings, identical equipment and logistics represent with identical reference, wherein, 1 is comprising propane and two
The feed stream of methyl ether, 2 is organic oxygen-containing compound or its aqueous solution logistics, and 3 is current, and 4 is that gas phase refines propylene oxide stream, 5
It is the refined propylene oxide stream of condensation, 6 is the refined propylene oxide stream of dehydration, and 7 is refined propylene oxide stream, and 8 is the refined propylene oxide stream of backflow, 9
It is refined bromopropane product logistics, 10 is that outer row washs water logistics, and 11 is the current of removing, and 12 is comprising dimethyl ether and organic oxygen-containing
The logistics of compound, 13 is tower reactor reboiler feed stream, and 14 is tower reactor reboiler output streams, and 15 is primary purification propane thing
Stream, 16 is intersegmental phase propane logistics, and 17 is intersegmental liquid phase propylene oxide stream, and 18 is the intersegmental liquid phase propylene oxide stream after supercharging；19
For water logistics are washed in reuse, 20 is organic oxygen-containing compound logistics, intersegmental liquid phase propylene oxide stream and reuse washing water logistics mixing
Logistics afterwards, 21 is the mixing logistics after supercharging, and E1 is overhead condenser, and E2 is tower reactor reboiler, and V is a point water return tank, P1
It is backflow propane booster pump, P2 is intersegmental liquid phase propane booster pump, and A is the first tower, and B is the second tower, and I is that dimethyl ether removes section,
II is washing section.
Specific embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
Embodiment 1
Feed stream comprising propane and dimethyl ether is obtained by oxygenatedchemicals olefin hydrocarbon, feed stream flow is
The content of 4t/h, wherein dimethyl ether is 45wt%, the also propylene containing 0.25wt%.
The single column technological process as shown in accompanying drawing 1 of propane subtractive process is carried out, and wherein washing section II is located at dimethyl ether removing section I
Top, dimethyl ether removing section I and washing section II between be provided with hydrops groove and riser.
Dimethyl ether removing treatment is completed in dimethyl ether removing section I, I points of dimethyl ether removing section is upper part, middle part and
Lower part, comprises the following steps：From under dimethyl ether removing section I the feed stream comprising propane and dimethyl ether is passed through at the top of part
1, organic oxygen-containing compound logistics 2 is passed through at the top of part from this section, it is passed through backflow refined third from the top of this section of upper part
Alkane logistics 8, from the primary purification propylene oxide stream (not marked in accompanying drawing) that dimethyl ether removing section top obtains, tower reactor is obtained comprising two
The logistics of methyl ether and organic oxygen-containing compound, the logistics is divided into two parts, wherein tower reactor reboiler feed stream 13 through tower reactor again
The E2 heating of boiling device obtains tower reactor reboiler output streams 14 and is circulated, and remainder is comprising dimethyl ether and organic oxygen-containing chemical combination
Oxygenatedchemicals olefin hydrocarbon apparatus are delivered in the logistics 12 of thing, the raw material as course of reaction；
Washing process is completed in washing section II, is comprised the following steps：Primary purification propylene oxide stream is entered by riser
Enter from washing section II bottoms, current 3 enter from washing section II tops, the refined propane thing of gas phase is obtained at the top of washing section II
Stream 4, washing section II bottoms obtain outer row after washing water logistics are collected by hydrops groove；
Dewater treatment is completed in point water return tank, is comprised the following steps：The refined propylene oxide stream 4 of gas phase passes through overhead condensation
Obtain condensing refined propylene oxide stream 5 after device E1 condensations, be dehydrated by point water return tank V and obtain being dehydrated refined propylene oxide stream 6 and take off
The current 11 for removing, wherein the refined propylene oxide stream 6 of dehydration turns into refined propylene oxide stream 7 after the propane booster pump P1 that flows back is pressurized,
The top that refined propylene oxide stream 7 is partly refluxed to dimethyl ether removing section I turns into the refined propylene oxide stream 8 of backflow, (namely dimethyl ether
The top of part in removing section, similarly hereinafter), remaining is produced as refined bromopropane product logistics 9, the current 11 of removing and comes from product
Discharged as outer row washing water logistics 10 after the washing water logistics mixing of liquid bath.
Wherein the operating pressure of tower top is 1.33MPa absolute pressures, and the operation temperature of tower top is 39.1 DEG C of (dimethyl ether removing sections
The temperature at top is 38.3 DEG C), and the operation temperature of tower reactor is 137.4 DEG C, and the number of theoretical plate of dimethyl ether removing section is 20 pieces,
It it is 4 pieces with the number of theoretical plate of washing section, wherein feed stream is extracted from the 16th piece of theoretical Board position charging of dimethyl ether removing section
Distillation solvent feeds from the 4th piece of theoretical Board position of dimethyl ether removing section, used as the organic oxygen-containing compound of extraction distillation solvent
It is acetone and the mixture of methyl alcohol, wherein content of acetone is the mass flow ratio of 3wt%, organic oxygen-containing compound and feed stream
It is 5.9, current are 0.25 with the mass flow ratio of feed stream, the operating reflux ratio of tower is 1.82.The material of the technological process
Balance is as shown in table 1.
The material balance result of the embodiment 1 of table 1
Data understand, by the inventive method, can have from the feed stream comprising propane and dimethyl ether as shown in Table 1
Effect removing dimethyl ether, the total oxide content of the refined bromopropane product logistics of gained is 58mg/kg, and wherein methanol content is 5mg/
Kg, logistics 12 of the gained comprising dimethyl ether and organic oxygen-containing compound can introduce oxygenatedchemicals olefin hydrocarbon apparatus, and as anti-
Answer the raw material of process.
Embodiment 2
Feed stream comprising propane and dimethyl ether is obtained by oxygenatedchemicals olefin hydrocarbon, flow is 3.2t/h, its
The content of middle dimethyl ether is 38wt%, the also component of carbon four of the propylene containing 0.15wt% and 0.8wt%.
Single column technological process of the propane subtractive process as shown in accompanying drawing 2 is carried out, with the basic class of the technological process of embodiment 1
Seemingly, main difference part is：Hydrops groove and riser are not set between dimethyl ether removing section I and washing section II, from washing section bottom
The washing water logistics of portion's outflow are flowed directly to the top that dimethyl ether removes section.
Wherein, the operating pressure in tower is 1.63MPa absolute pressures (tower top pressure), and the operation temperature of tower top is 49.5 DEG C
(temperature at the top of dimethyl ether removing section is 47.2 DEG C), and the operation temperature of tower reactor is 140.3 DEG C, and dimethyl ether removes the reason of section
It is 17 pieces by plate number, and the number of theoretical plate of washing section is 4 pieces, wherein feed stream removes the 15th piece of theoretical plate of section from dimethyl ether
Position feeds, and extraction distillation solvent feeds from the 4th piece of theoretical Board position of dimethyl ether removing section, used as having for extraction distillation solvent
Machine oxygenatedchemicals is methyl alcohol, and the mass flow ratio of organic oxygen-containing compound and feed stream is 5.6, current and feed stream
Mass flow ratio is 0.29, and the operating reflux ratio of tower is 1.21.The material balance of the technological process is as shown in table 2.
The material balance result of the embodiment 2 of table 2
Data understand, by the inventive method, can have from the feed stream comprising propane and dimethyl ether as shown in Table 2
Effect removing dimethyl ether, the total oxide content of the refined bromopropane product logistics of gained is 31mg/kg, and wherein methanol content is 3mg/
Kg, logistics 12 of the gained comprising dimethyl ether and organic oxygen-containing compound can introduce oxygenatedchemicals olefin hydrocarbon apparatus, and as anti-
Answer the raw material of process.
Embodiment 3
Feed stream comprising propane and dimethyl ether is obtained by oxygenatedchemicals olefin hydrocarbon, feed stream flow is
The content of 1.2t/h, wherein dimethyl ether is 2wt%, and the also component of carbon four of the propylene containing 0.3wt% and 1.1wt%.
Double tower process flow of the propane subtractive process as shown in accompanying drawing 3 is carried out, including the first tower A and the second tower B, wherein the
One tower includes that dimethyl ether removes section I, and the second tower includes washing section II.Concrete technology flow process is as follows：
Dimethyl ether removes treatment and is completed in the second tower B, and dimethyl ether removes section I points for upper part, middle part and lower part,
Comprise the following steps：The feed stream 1 comprising propane and dimethyl ether, the part from this section are passed through from the top of the pars infrasegmentalis point
Top is passed through the aqueous solution logistics 2 of organic oxygen-containing compound, and the refined propylene oxide stream 8 of backflow is passed through from the top of this section of upper part,
From the primary purification propylene oxide stream 15 that this section of top obtains, the thing containing dimethyl ether and organic oxygen-containing compound is obtained from the tower tower reactor
Stream a, logistics part is circulated through tower reactor reboiler E2, and remainder delivers to oxygenatedchemicals olefin hydrocarbon apparatus, as anti-
Answer the raw material of process；
Washing process is completed in the first tower A, is comprised the following steps：Primary purification propylene oxide stream 15 enters from the tower bottom
Enter, current 3 enter from the top of tower, the refined propylene oxide stream 4 of gas phase, the washings thing that the tower tower reactor is obtained are obtained in the top of tower
Stream discharge；
Dewater treatment is completed in point water diversion cans, is comprised the following steps：The refined propylene oxide stream 4 of gas phase passes through overhead condensation
Obtain condensing refined propylene oxide stream 5 after device E1 condensations, be dehydrated by point water return tank V and obtain being dehydrated refined propylene oxide stream 6 and take off
The current 11 for removing, wherein the refined propylene oxide stream 6 of dehydration is partly refluxed to dimethyl ether and takes off after the propane booster pump P1 that flows back is pressurized
Except the top of section I, remaining is produced as refined bromopropane product logistics 9.
Wherein the operating pressure of the first column overhead is 2.95MPa absolute pressures, and the operation temperature of the first column overhead is 76.0 DEG C,
Be 166.2 DEG C with the operation temperature of the second tower tower reactor, and the number of theoretical plate of dimethyl ether removing section is 12 pieces, and washing section theory
Plate number is 3 pieces, and from the 11st piece of section theoretical Board position charging of dimethyl ether removing, extraction distillation solvent is from diformazan for wherein feed stream
4th piece of theoretical Board position charging of ether removing section, is methanol aqueous solution as the organic oxygen-containing compound of extraction distillation solvent, its
Middle methanol content is 94wt%, and the mass flow ratio of organic oxygen-containing compound and feed stream is 0.71, current and feed stream
Mass flow ratio be 1, the operating reflux ratio of tower is 0.51.The material balance of the technological process is as shown in table 3.
The material balance result of the embodiment 3 of table 3
Data understand, by the inventive method, can have from the feed stream comprising propane and dimethyl ether as shown in Table 3
Effect removing dimethyl ether, the total oxide content of the refined bromopropane product logistics of gained is 36mg/kg, and wherein methanol content is 3mg/
Kg, logistics 12 of the gained comprising dimethyl ether and organic oxygen-containing compound can introduce oxygenatedchemicals olefin hydrocarbon apparatus, and as anti-
Answer the raw material of process.
Embodiment 4
Feed stream comprising propane and dimethyl ether is obtained by oxygenatedchemicals olefin hydrocarbon, feed stream flow is
The content of 1.8t/h, wherein dimethyl ether is 5wt%, the also component of carbon four of the propylene containing 0.2wt% and 1.3wt%.
Double tower process flow of the propane subtractive process as shown in accompanying drawing 4 is carried out, including the first tower A and the second tower B, wherein the
One tower A includes the upper part of washing section II and dimethyl ether removing section I, and is provided with hydrops groove and riser, second therebetween
Tower B includes the middle part and lower part of dimethyl ether removing section I, and concrete technology flow process is as follows：
In the second tower B, the feed stream comprising propane and dimethyl ether is passed through from the top of dimethyl ether removing pars infrasegmentalis point
1, the intersegmental liquid phase propylene oxide stream after being passed through organic oxygen-containing compound logistics 2 and supercharging at the top of part from dimethyl ether removing section
18, the logistics comprising dimethyl ether and organic oxygen-containing compound is obtained from the tower tower reactor, a logistics part is through tower reactor reboiler E2
It is circulated, remainder delivers to oxygenatedchemicals olefin hydrocarbon apparatus, the raw material as course of reaction；
In the first tower A, intersegmental phase propane logistics 16 is passed through from the bottom of part in dimethyl ether removing section, backflow is refined
Propylene oxide stream 8 is added from the top of part in dimethyl ether removing section, and the intersegmental liquid phase propylene oxide stream 17 of tower tower reactor discharge passes through
After intersegmental liquid phase propane booster pump P2 superchargings, dimethyl ether removes the top of part in section in the second tower B of addition；From dimethyl ether removing
The primary purification propylene oxide stream (not marked in accompanying drawing) that atop part is obtained in section enters the bottom of washing section II by riser,
Current 3 enter from the top of washing section II, obtain the refined propylene oxide stream 4 of gas phase at the top of washing section II, washing section II bottoms by
Hydrops groove to be collected arranged outside the washing water logistics for obtaining and mix with the current 11 of removing and discharged as outer row washing water logistics 10；
Dewater treatment is completed in point water diversion cans, is comprised the following steps：The refined propylene oxide stream 4 of gas phase passes through overhead condensation
Obtain condensing refined propylene oxide stream 5 after device E1 condensations, be dehydrated by point water return tank V and obtain being dehydrated refined propylene oxide stream 6 and take off
The current 11 for removing, wherein the refined propylene oxide stream 6 of dehydration is partly refluxed to dimethyl ether and takes off after the propane booster pump P1 that flows back is pressurized
Except the top of section I, remaining is produced as refined bromopropane product logistics 9.
Wherein the operating pressure of the first column overhead is 1.73MPa absolute pressures, and the operation temperature of the first column overhead is 52.8 DEG C,
Be 150.2 DEG C with the operation temperature of the second tower tower reactor, and the number of theoretical plate of dimethyl ether removing section is 16 pieces, and washing section theory
Plate number is 3 pieces, and from the 13rd piece of section theoretical Board position charging of dimethyl ether removing, extraction distillation solvent is from diformazan for wherein feed stream
4th piece of theoretical Board position charging of ether removing section, is methyl alcohol, organic oxygen-containing as the organic oxygen-containing compound of extraction distillation solvent
Compound is 2 with the mass flow ratio of feed stream, and current are 0.75 with the mass flow ratio of feed stream, and the operation of tower flows back
Than being 0.65.The material balance of the technological process is as shown in table 4.
The material balance result of the embodiment 4 of table 4
As shown in Table 4 knowable to data, by the inventive method, dimethyl ether, gained can be effectively removed from feed stream
The total oxide content of the feed stream after refined is 50mg/kg, and wherein methanol content is 3mg/kg, gained comprising dimethyl ether and
The logistics 12 of organic oxygen-containing compound can introduce oxygenatedchemicals olefin hydrocarbon apparatus, and the raw material as course of reaction.
Embodiment 5
Feed stream comprising propane and dimethyl ether is obtained by oxygenatedchemicals olefin hydrocarbon, feed stream flow is
The content of 2t/h, wherein dimethyl ether is 20wt%, the component of carbon four also containing 1.5wt%.
Double tower process flow of the propane subtractive process as shown in accompanying drawing 5 is carried out, with the basic class of the technological process of embodiment 4
Seemingly, main difference part is：Come from the reuse washing water logistics 19 and organic oxygen-containing compound stream 2 of outer row's washing water logistics
And form organic oxygen-containing compound logistics, intersegmental liquid phase propylene oxide stream and reuse washing after the intersegmental mixing of liquid phase propylene oxide stream 17
The mixed logistics 20 of water logistics, the logistics turns into the mixing logistics after supercharging after being pressurized through intersegmental liquid phase propane booster pump P2
21, add the top (embodiment 4 is without row's washing water logistics outside reuse) of part in dimethyl ether removing section.
Wherein the operating pressure of the first column overhead is 1.8MPa absolute pressures, and the operation temperature of the first column overhead is 52.9 DEG C,
Be 146.5 DEG C with the operation temperature of the second tower tower reactor, and the number of theoretical plate of dimethyl ether removing section is 15 pieces, and washing section theory
Plate number is 4 pieces, and from the 12nd piece of section theoretical Board position charging of dimethyl ether removing, extraction distillation solvent is from diformazan for wherein feed stream
5th piece of theoretical Board position charging of ether removing section, is methanol aqueous solution as the organic oxygen-containing compound of extraction distillation solvent, its
Middle methanol content is 95.7wt%, and the mass flow ratio of organic oxygen-containing compound and feed stream is 2.2, current and feed stream
Mass flow ratio be 0.65, the operating reflux ratio of tower is 1.15.The material balance of the technological process is as shown in table 5 and table 6.
The material balance result 1 of the embodiment 5 of table 5
The material balance result 2 of the embodiment 5 of table 6
From table 5 and data shown in table 6, by the inventive method, dimethyl ether effectively can be removed from feed stream,
The total oxide content of the feed stream after gained is refined is 26mg/kg, and wherein methanol content is 1mg/kg, and gained includes diformazan
The logistics 12 of ether and organic oxygen-containing compound can introduce oxygenatedchemicals olefin hydrocarbon apparatus, and the raw material as course of reaction.
Embodiment is respectively calculated more than, by technical scheme, the raw material thing comprising propane and dimethyl ether
Propane in stream has obtained refined well, and obtained refined propane can be used as the raw material of dehydrogenating propane or light hydrocarbon cracking,
Can be used as liquefied petroleum gas, the value of feed stream is thus greatly improved.
Claims (10)
1. it is a kind of from the feed stream comprising propane and dimethyl ether refine propane technique, it is characterised in that the technique according to
It is secondary that the feed stream comprising propane and dimethyl ether is carried out into dimethyl ether removing treatment, washing process and dewater treatment；
The dimethyl ether removing treatment is completed in dimethyl ether removes section (I), and dimethyl ether removes section (I) and is divided into part, middle part
Divide and lower part, comprise the following steps：Feed stream (1) comprising propane and dimethyl ether is extracted from its top feed of lower part
Its top feed of distillation solvent logistics therefrom part, refined its top feed of the propylene oxide stream (8) from upper part of backflow, through extraction essence
Evaporate and primary purification propylene oxide stream is obtained at the top of upper part, lower section bottom is obtained comprising dimethyl ether and extraction distillation solvent
Logistics a, logistics part is circulated through tower reactor reboiler (E2), and remainder delivers to next workshop section；
The washing process is completed in washing section (II), is comprised the following steps：Primary purification propylene oxide stream is from washing section (II)
Bottom feed, current (3) obtain gas phase through continuous flow upstream washing from washing section (II) its top feed at the top of washing section (II)
Refined propylene oxide stream (4), washing section (II) bottom obtains washing water logistics；
The dewater treatment is completed in point water return tank (V), is comprised the following steps：Gas phase refines propylene oxide stream (4) and leads to successively
Overhead condenser (E1) and point water return tank (V) are crossed, obtains being dehydrated refined propylene oxide stream (6) after dehydration, it passes through backflow third
After alkane booster pump (P1) supercharging, the top that dimethyl ether removes part in section (I) is partly refluxed to, remaining is used as refined bromopropane product
Logistics (9) is produced, the current (11) of point water return tank (V) bottom discharge removing.
2. it is according to claim 1 it is a kind of from the feed stream comprising propane and dimethyl ether refine propane technique, its
It is characterised by, the technique is operated using single column, wherein washing section (II) is located at the top of dimethyl ether removing section (I)；
Described washing water logistics directly flow to the top that dimethyl ether removes part in section (I) from washing section (II) bottom；
Or remove setting hydrops groove and riser, the preliminary essence between section (I) and washing section (II) in described dimethyl ether
Propylene oxide stream processed enters washing section (II) bottom by riser, and the washing water logistics that washing section (II) bottom obtains are by hydrops groove
Outer row or part overflow remove the top of part in section (I) to dimethyl ether after collection.
3. it is according to claim 1 it is a kind of from the feed stream comprising propane and dimethyl ether refine propane technique, its
It is characterised by, the technique is operated using double tower；
Dimethyl ether wherein is removed into section (I) to be arranged in the second tower (B), washing section (II) is arranged in the first tower (A), washing section
(II) arranged outside the washing water logistics that bottom obtains；
Or, lower part and middle part that dimethyl ether removes section (I) are arranged in the second tower (B), dimethyl ether removing section (I)
Upper part and washing section (II) are arranged in the first tower (A), and washing section (II) is located at dimethyl ether and removes the upper of part on section (I)
Just, and removed between section top is divided in washing section (II) and dimethyl ether and set hydrops groove and riser, wherein leaving dimethyl ether removing
In section the primary purification propylene oxide stream of atop part by riser enter washing section (II) bottom, washing section (II) bottom by
Hydrops groove collected and arranged outside the washing water logistics for obtaining, and the intersegmental liquid phase propylene oxide stream (17) of the first tower (A) tower reactor uses intersegmental liquid phase
After propane booster pump (P2) supercharging, the top of part in the second tower (B) dimethyl ether removing section is added to.
4. according to a kind of any described works that propane is refined from the feed stream comprising propane and dimethyl ether of claim 1-3
Skill, it is characterised in that described washing water logistics mix with the current (11) of removing washs water logistics (10) discharge as outer row.
5. it is according to claim 4 it is a kind of from the feed stream comprising propane and dimethyl ether refine propane technique, its
It is characterised by, described outer row washs after water logistics (10) partly or entirely mix with extraction distillation solvent logistics and enters dimethyl ether
The top of part in removing section (I)；Or described washings stream portions or after all mixing with extraction distillation solvent logistics
The top of part in section (I) is removed into dimethyl ether；Or removing current (11) partly or entirely with extraction distillation solvent thing
Enter the top that dimethyl ether removes part in section (I) after stream mixing.
6. according to any described a kind of refined from the feed stream comprising the propane and dimethyl ether propane of claims 1 to 3
Technique, it is characterised in that described extraction distillation solvent logistics is organic oxygen-containing compound or its aqueous solution logistics (2), extraction
Organic oxygen-containing compound in distillation solvent logistics is selected from one or more in methyl alcohol, ethanol, isopropanol, acetone, preferably
Methyl alcohol and/or acetone, when with organic oxygen-containing compound aqueous solution form application, the organic oxygen-containing compound of the aqueous solution
Mass content >=85wt%, preferably >=93wt%.
7. according to any described a kind of refined from the feed stream comprising the propane and dimethyl ether propane of claims 1 to 3
Technique, it is characterised in that the described feed stream (1) comprising propane and dimethyl ether comes from oxygenatedchemicals alkene mistake
Journey, including propane, dimethyl ether, carbon two, propylene and the component of carbon four, the wherein content of dimethyl ether are 1-60wt%, preferably 2-
45wt%.
8. according to any described a kind of refined from the feed stream comprising the propane and dimethyl ether propane of claims 1 to 3
Technique, it is characterised in that it is 1.1~3.5MPa that the dimethyl ether removes section (I) and the operation absolute pressure of washing section (II), excellent
Select 1.3~3.0MPa；Operation temperature is 31~198 DEG C, preferably 38~165 DEG C；Reflux ratio be 0.3~2.5, preferably 0.5~
1.9。
9. according to any described a kind of refined from the feed stream comprising the propane and dimethyl ether propane of claims 1 to 3
Technique, it is characterised in that the theoretical cam curve of dimethyl ether removing section (I) is 10~26 pieces, preferably 12~20 pieces；The water
The theoretical cam curve for washing section (II) is 2~6 pieces, preferably 3~4 pieces.
10. according to any described a kind of refined from the feed stream comprising the propane and dimethyl ether propane of claims 1 to 3
Technique, it is characterised in that the organic oxygen-containing compound in the extraction distillation solvent logistics and the original comprising propane and dimethyl ether
The mass flow ratio of material stream (1) is 0.5~8, preferably 0.7~6；The current (3) and the raw material comprising propane and dimethyl ether
The mass flow ratio of logistics (1) is 0.15~2, preferably 0.25~1.
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| CN110205168A (en) * | 2019-05-15 | 2019-09-06 | 沈阳瑞鸿能源环保科技有限公司 | The formula and preparation process and method for concentration of a kind of dimethyl ether new energy |
| CN110330413A (en) * | 2019-07-31 | 2019-10-15 | 惠生工程（中国）有限公司 | A method of propylene glycol monomethyl ether in recycling alcohol ether aqueous solution logistics |
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